Homopolymerization of benzyl compounds



Patented Nov. 1, 1949 HOMOPOLYMERIZATION OF BENZYL COMPO UNDS Charles F.Feasley, Woodbury, and Howard D.

Hartough, Pitman, N..J., assign or: to Socony- Vacuum Oil Company,Incorporated, a corporation of New York No Drawing. Application April 7,1945, Serial No. 587,206

4 Claims.

The present invention relates to a method of producing resinous bodies,and more particularly, to a method of making resinous bodies fromaromatic oxy-compounds, especially aromatic alcohols and ethers, and tothe products thereof.

It is well known that aromatic alcohols having either a saturated sidechain or an unsaturated side chain, such as benzyl or cinnamic alcoholscan be polymerized to form resinous bodies by such agents as sulfuricacid, phosphorous acid or phosphorus pentoxide. It is also known thatbenzyl alcohol is readily converted to a yellow resinous hydrocarbon bycontact in the vapor phase with precipitated alumina at temperaturesabove 300 C.

It has now been discovered that mono-nuclear and polynuclear aromaticalcohols and ethers such as benzyl alcohol, benzyl ether, trimethylbenzyl alcohols, trimethyl benzyl ethers, and especially polyalkylaralkyl alcohols and ethers of the aromatic constituents of aromaticpetroleum stocks, can be converted into resinous products in a liquidphase at temperatures below 300 C.

As those skilled in the art know, large quantities of aromatic petroleumstocks are available. The aromatic constituents of these aromaticpetroleum stocks can be converted into the corresponding alcohols andethers in various ways. Thus, for example, aromatic petroleum stocksderived from Houdry cracking operations and having boiling point rangesvarying from 150 C. to 210 C. contain between 50 per cent and 75 percent of aromatic hydrocarbons of the polyalkyl benzene type. One ofthese stocks, for example, is believed to be, primarily, polymethylbenzenes ranging from trimethyl benzene to tetramethyl benzene. Smallamounts of other aromatic hydrocarbons, such as ethyl methyl benzenealso may be present. There are three trimethyl benzenes, mesitylene,1,3,5-trimethyl benzene; pseudocumene or 1,2,4-trimethyl benzene; andhemimellitene or 1,2,3-trimethyl benzene. There are three tetramethylbenzenes, durene or 1,2,4,5- tetramethyl benzene; isodurene or 1,2,3,5-tetramethyl benzene; and prehnitene, 1,2,3,4-tetramethyl benzene.All of these polyalkyl benzenes are present in the various stocks,boiling between 310 degrees and 395 degrees F. to a greater or lesserdegree. The higher boiling cuts of these aromatic stocks, for examplethose with an initial boiling point of 210 0., contain appreciablequantities of monoand polyalkyl polynuclear aromatic hydrocarbons suchas monoand di-methyl naphthalene.

The aromatic petroleum stocks can be treated to produce thecorresponding alcohols, for example, by haloalkylation to thecorresponding aralkyl chlorides and the aralkyl chlorides converted tothe corresponding alcohol's or to ethers. A method of haloalkylatingaromatic petroleum stocks is disclosed in the co-pending United Statesapplication Serial No. 515,145, filed December 21, 1943, in the name ofHoward D. Hartough, now abandoned. A method of converting the aromaticconstituents of aromatic petroleum stocks to alcohols and ethers isdisclosed in the co-pending United States application for Letters PatentSerial No. 560,365, now abandoned. Aromatic alcohols, ethers and aralkylesters of hydroxy carboxylic acids, whether produced in the mannerdescribed therein or by other methods and whether derived from aromaticpetroleum stocks or otherwise, can be converted into resinous bodies ina liquid phase operation not employing any of the conventionalcondensation agents, sulfuric acid, phosphorous acid or the like.

The present method provides satisfactory results when employing aralkylalcohols of mononuclear or polynuclear aromatic compounds whether thehydroxyl group be attached to the ring by a saturated or unsaturatedalkyl chain. Typical of such aromatic alcohols are benzyl and cinnamicalcohols. Aralkvl alcohols having alkyl substituted rings likewisereadily lend themselves to condensation by the present method.illustrative of such alkyl substituted mono-nuclear aralkyl alcohols arehemimellitenyl alcohol and its isomers and durenyl alcohol and itsisomers. Both of the foregoing homologues are grouped together aspolyalkyl benzyl alcohols. Among the polynuclear aralkyl alcohols whichlikewise may be condensed by the present method are the alcohols whichare derivatives of naphthalene and monoand polyalkyl naphthalene. It isto be understood that the present method is not limited to the treatmentof methyl substituted aralkyl alcohols but also provides satisfactoryresults with monoand polyalkyl monoand polynuclear arallwl alcohols inwhich the alkyl groups substituted in the ring are other than methyl,for example, ethyl, methyl and ethyl radicals, and in general radicalshaving up to 24 carbon atoms.

The present process produces satisfactory results when aralkyl ethersare treated. Thus, for example, benzyl ether, (CoHsCHz) :0 may becondensed as well as polyalkyl benzyl ether according to the presentmethod. Ethers of monoand polyalkyl polynuclear carbocyclic compoundssuch as (CroHvCI-Iz) 2O, (CHaCrcHoCHnhO and alcohol may be condensedwith durenyl alcohol or benzyl ether with polyalkyl benzyl ether. Ac-

cordingly, in view of the source of the reactants,

described hereinbefore, the reactants of the present invention may bedefined as benzyl alcohols having not more than 4 nuclear hydrogenatoms.

replaced with methyl groups, dibenzyl ethers having not more than 4nuclear'hydrogen atoms replaced with methyl groups, and benzyl lactatesJ having not more than 4 nuclear hydrogen atoms replaced with methylgroups, the hydrogen atoms of said benzyl alcohols, dibenzyl ethers, andbenzyl lactates being otherwise unsubstituted.

It is an object of the present invention to provide a method ofcondensing aralkyl alcohols, aralkyl ethers and aralkyl esters ofhydroxy carboxylic acids in a liquid phase reaction employing a solidcatalyst. It is another object of the present invention to provide amethod of producing resinous bodies from aralkyl alcohols, aralkylethers and aralkyl esters of hydroxy carboxylic acids in a liquid phasereaction employing natural or synthetic hydrated aluminum hydroxysilicates. It is a further object of this invention to provide a methodof producing resinous bodies from aralkyl alcohols, aralkyl ethers andaralkyl esters of carboxylic acids in a liquid phase reaction employingnatural or synthetic clays. The present invention also has as an objectthe provision of a method of producing resinous bodies from aralkylalcohols, aralkyl ethers and aralkyl esters of hydroxy carboxylic acidemploying natural and synthetic clays of the montmorillonite type. Thepresent invention likewise has as an object the provision of a method ofproducing resinous bodies from aralkyl alcohols, aralkyl ethers andaralkyl esters of hydroxy carboxylic acids employing natural orsynthetic clays of the activated montmorillonite type. Other objects andadvantages of this invention will become apparent to those skilled inthe art after reading the following description.

In accordance with the method of this invention aralkyl alcohols, ethersor aralkyl esters of hydroxy carboxylic acids are condensed by heatingthe alcohols, ethers or esters in liqu d phase in the presence of asolid condensation catalyst. The condensation reaction may be carriedout in the presence or absence of a solvent or diluent at temperaturesbelow the boiling point of the reaction mass. The reaction time is ofthe order of about an hour to several hours. After the reaction iscomplete the reaction liquid is treated to remove the condensationagent. The solid condensation agent is most readily removed byfiltration or contrifugation. The solid condensation catalyst is usuallywashed with suitable organic solvents to remove resins or oils adsorbedon the clay. When desirable the solid condensation agent or catalyst canbe re-used after activation.

The novel catalyst or condensation agent is is a solid adsorbent contactmass such as clays of the activated montmorillonite type, fresh burntAttapulgus clay, silica gel, synthetic aluminasilica gelcatalystscontaining about '1 per cent to about 15 per cent alumina,powdered cracking catalyst which is a base exchanged silicaaluminacatalyst containing about '1 per cent to about 15 per cent alumina andsimilar adsorbent materials. The condensation agent is used preferablyin finely-divided or powdered form. Illustrative of the clays of themontmorillonite type which have provided satisfactory results is anon-swelling crystalline rather than amorphous bentonite clay which hasbeen activated by an acid treatment in a manner well known to thoseskilled in the art to give a composition approaching AhSi4Oio(OH)a-nH:O.The term hydrated aluminum hydroxy silicate is used hereinafter toinclude-all of the catalysts or condensing agents disclosed herein.

Those skilled in the art will instantly recognize that the use of asolid condensation agent in this reaction provides at least twoimportant advantages over the prior art condensation agents as will bemore readily appreciated by consideration of the following discussion.

Heretofore the most generally used of the known condensation agents forthe condensation of benzyl alcohol and cinnamic alcohols have been theacid catalysts, sulfuric acid and various acids of phosphorus. The knowncondensation agents for thispurpose are liquids miscible with thereaction mass. Consequently, it has been very difficult in the past toseparate the acid condensation agent from the resinous material. Indistinct contrast the novel condensation agents of the present inventionare readily and cheaply separated from the reaction mass.

The present condensation agents provide a second and equally importantadvantage over prior art agents for the purposes of the presentinvention. Due to the character of the prior art, soluble, acidiccondensation agents, the prior art condensation agents were useless forfurther employment as catalysts in the condensation reaction. On theother hand, the novel condensation agents are readily re-activated andprepared for re-use. The novel condensation agents of this invention canbe readily regenerated or re-activated by methods known to those skilledin the art.

In addition to the foregoing advantages which the solid condensationagents of this invention possess in contrast to the prior art liquidagents, the solid condensation agents of this invention entrain darkcolored materials present in the reaction and remove these coloringmatters from.

the resinous reaction products when the solid condensation agents areseparated from the reaction mass in any suitable manner. As a result ofthis absorption or entrainment, the resinous materials thus produced aremuch lighter in color than prior art products prepared by condensating,for example, aralkyl alcohols such as benzyl alcohol using the prior artliquid acidic condensation agents. To further improve the color, theresin may be dissolved in a suitable solvent and filtered a second timethrough freshly activated natural hydrated aluminum hydroxy silicateclay using about 10 per cent by weight based upon the weight of theresin solution. The amount of clay employed for the second filtrationmay vary from about 10 per cent by weight to the amount necessary foruse as a catalyst for another batch, say about 30 per cent to about 35per cent by weight. This clay, used only for decolorization, may be usedas the catalyst for another batch if so desired without reactivation.

The following examples are provided for the EXAMPLE I Benzyl alcohol Aresin has been prepared from benzyl alcohol in the following manner inaccordance with the principles of the present invention.

One hundred and fifty (150) grams, about 144 cubic centimeters, (1.4moles) of benzyl alcohol, 77.5 grams of Stoddard solvent (safety solventnaphtha; boiling point 300 F. to 400 F.) about 0.7 volume and 60 gramsof clay of the montmorillonite type which is a hydrated aluminum hydroxysilicate were stirred together at atmospheric pressure for 12 hours at110 C. The reaction mixture was filtered and the filtrate distilled ortopped to a pot temperature of 233 C. at 12 millimeters of mercurypressure to remove solvent, unreacted alcohol and intermediate resinsvolatile at this temperature. The still residue amounted to 24.5 gramsof a brownish-red, tacky, tough solid.

EXAMPLE II Trimethz Z benzyl alcohols One hundred and fifty grams, above149.5 cubic centimeters, (1 mole) of trimethyl benzyl alcohols from apetroleum naphtha having a boiling range of 310 F., to 395 F., 77.5grams (0.7 volume) of Stoddard solvent and 60 grams of clay of themontmorillonite type were stirred at 110 C. under atmospheric pressurefor 12 hours. At the end of this period the reaction mixture or mass wasfiltered and the filtrate distilled or topped to a pot temperature of300 C. at 7 millimeters of 'mercury pressure to remove solvent,unreacted alcohols and intermediate resin. Fifty-four grams ofreddish-amber, hard, brittle resin was obtained as a still residue.

EXAMPLE III Benzyl Ether EXAMPLE IV Trimethyl benzyl ether Five hundredand sixty grams, about 571 cubic centimeters (about 2.0 moles) oftrimethyl benzyl ether derived from a petroleum naphtha having a boilingrange of 310 F., to 395 F., and 150 grams of re-activated Super Filtrol"clay which is a hyd'rated aluminum hydroxy silicate (freshly activatedat 1050 F.) were stirred together at atmospheric pressure for 2.5 hoursat 200 C. to 225 C. The reaction mixture was filtered and the claywashed with a solvent [Sovasol #74 (predominantly xylenes) The filtratewas topped to a pot temperature of 300 C. at a pressure of 4 millimetersof mercury to remove solvent, unreacted ether and intermediate resin.Three hundred and sixty-six grams of still residue remained which was abrittle reddish amber resin.

6 EXAMPLE v Twenty-two and two-tenths grams (0.1 mole) of trimethylbenzyl lactates (made by a standard procedure from trimethyl benzylchlorides and sodium lactate), 50 cubic centimeters of Stoddard solventand 10 grams of natural hydrated aluminum hydroxy silicate clay wereheated and stirred together at atmospheric pressure for 11 V2 hours atll0i5 C. The reaction mixture was filtered and the clay washed withbenzol. The combined filtrates were distilled to give in addition torecovered trimethyl benzyl lacates and intermediate liquids, 11 grams(49.5 per cent conversion) of a light amber colored solid residue (finalpot temperature for topping-300 C. at 10 millimeters) which was hard andbrittle.

It is believed desirable to point out that when using a solvent thequantity thereof is not critical, sufiicient solvent being used toprovide a fluid reaction mass at the condensation temperature.Furthermore, the amount of condensation agent is not critical,suilicient being used to ensure intimate contact between all of theliquid reactant and the solid condensation agent. The amount ofcondensation agent preferably should be between 0.2 volume and about 0.7volume based on the volume of the hydroxy-, aralkyloxy-, or oxy-arylcompound, i. e. alcohol or ether or ester or about 0.1 part to about 0.5part by weight based on the weight of the material to be condensed.

The solid catalyst or condensation agent may be activated orreactivated, as those skilled in the art know, by heating in a kiln orother suitable apparatus at controlled temperatures in the presence ofsuitable amounts of air for oxidation of carbonaceous deposits.

Although the present invention has been described in conjunction withcertain preferred embodiments thereof, those skilled in the art willunderstand that variations and modifications can be made withoutdeparting from the principles thereof. Thus, for example, the principlesof the present invention may be employed to condense aralkyl compoundscontaining an ether linkage or a hydroxy radical such as, for example,aralkyl alcohols, aralkyl ethers and aralkyl esters of hydroxycarboxylic acids.

We claim: 7

1. The method ofefiecting the homopolymerization of an organic compoundselected from the group consisting of a benzyl alcohol having not morethan 4 nuclear hydrogen atoms replaced with methyl groups, a dibenzylether having not more than 4 nuclear hydrogen atoms replaced with methylgroups and a' benzyl lactate having not more than 4 nuclear hydrogenatoms replaced 7 with methyl groups, the hydrogen atoms of said benzylalcohol, said dibenzyl ether, and said benzyl lactate being otherwiseunsubstituted, which comprises heating said organic compound, in theliquid phase, in the presence of a hydrated aluminum hydroxy silicateclay catalyst, at temperatures below the boiling point of said organiccompound, for a period of time sufiicient to effect resinification.

2. The method of effecting the homopolymerization of benzyl alcohol,which comprises heating said benzyl alcohol, in the liquid phase, in thepresence of a hydrated aluminum hydroxy silicate clay catalyst, attemperatures below the boiling point of benzyl alcohol, for a period oftime sulficient to efiect resinification.

3. The method of efiecting the homopolymerization oi! trimethyl dibenzylether, which com- 7 prises heating said trimethyl dibenzyl ether, in theliquid phase, in the presence of a hydrated aluminum hydroxy silicateclay catalyst, at temperatures below the boiling point of trimethyldibenzyl ether, for a period of time sufiicient to efl'ectresiniflcation.

4. The method of eflecting the homopolymerization of trimethyl benzyllactate, which comprises heating said trimethvl benzyl lactate in theliquid phase, in the presence of a hydrated aluminum hydroxy silicateclay catalyst, at temperatures below the boiling point of trimethylbenzyl lactate, for a period of time suflicient to eflectresinification.

CHARLES F. FEASLEY. HOWARD D. HARTOUGH.

REFERENCES CITED The following references are of record in the file ofthis patent:

8 UNITED STATES PATENTS Number Name Date 2,097,348 Shipp Oct. 26, 19372,129,153 Schirm Sept. 6, 1938 2,319,386 Carmody May 8, 1943 2,334,565Lieber et a1 Nov. 16, 1943 FOREIGN PATENTS 10 Number Country Date516,936 Great Britain Jan. 16, 1940 Certificate of Correction Patent No.2,486,831 November 1, 1949 CHARLES F. FEASLEY ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows:

Column 5, line 29, for the word above read about;

and that the said Letters Patent should be read with this correctiontherein that the same may conform to the record of the case in thePatent Ofiice.

Signed and sealed this 9th day of May, A. D. 1950.

THOMAS F. MURPHY,

Assistant Commissioner of Patents.

